Estimation of Thermodynamic Models for Azeotropic Systems Using Data Assessment and Thermodynamic Consistency Test

Authors(2) :-Manojkumar M. S, B. Sivaprakash

Knowledge of precise vapor-liquid equilibria is a requirement to the detailed design of distillation equipment. However, such data is limited, and usually not available when new systems are under consideration, because it is complex and laborious to obtain the data experimentally. Predictive methods are therefore valuable for process evaluation and design. In this paper five binary azeotropes namely Acetone-water, Acetone-methanol, Ethanol-water, Ethanol-benzene, and Methanol-water were taken. The experimental vapour liquid equilibrium data determination for this system was carried out using Othmer type ebuilliometer in laboratory scale at atmospheric pressure. For the theoretical prediction of VLE five activity coefficient models namely NRTL, UNIQUAC, UNIFAC and modified form of florry-huggins equations (SRS and TCRS) have been employed. The parameters for the five systems of four models namely NRTL, UNIQUAC SRS and TCRS were computed using Newton Raphson technique. UNIFAC model was adopted using Analytical solution of group contribution (ASOG) method. Also these models are validated using thermodynamic consistency test. The performance of these models are tested and reported.

Authors and Affiliations

Manojkumar M. S
Department of Chemical Engineering, FEAT, Annamalai University, Annamalai Nagar, Tamil Nadu, India
B. Sivaprakash
Department of Chemical Engineering, FEAT, Annamalai University, Annamalai Nagar, Tamil Nadu, India

Vapour Liquid Equilibrium, Azeotrope, Non Ideal System, Activity Coefficient Model, Thermodynamic Consistency

  1. Anderson, T.F., J.M Prausnitz, 1978. Application of the UNIQUAC equation to calculation of multicomponent phase equilibria, Industrial and Engineering Chemistry Process Design and Development, 17 (4): 561-567.
  2. Fredenslund, A. , J. Gmehling, M.L. Michelson, P. Rasmussen, 1977. Computerized Design of Multicomponent Distillation Columns using the UNIFAC Group Contribution Method, Industrial and Engineering Chemistry Process Design and Development 16 (4): 450-462.
  3. Fredenslund, A., R.L. Jones, J.M. Prausnitz, 1975. Group-Contribution Estimation of Activity Coefficients in Nonideal Liquid Mixtures, American Institute of Chemical Engineering, 21(6): 1086-1099.
  4. Gadekar, S. V., R. V. Naik, J. D. Bapat, 2004. Acetic Acid-Water-Toluene System Batch Distillation Parameters for Heterogeneous Azeotropic systems, Chemical Engineering World, 44.
  5. Geankoplis, C.J., 2003. Transport Process and Separation Process, Prentice Hall Publication, New Jersey.
  6. Hilmen, E.K., 2000. Separation of Azeotropic Mixtures Tools for Analysis and Studies on Batch Distillation Operation, Phd thesis, Norwegian University of Science and Technology.
  7. Kannan, A., 2003. Short Term Training Programme on Modelling, Simulation and Analysis of Enhanced Distillation Process, Indian institute of technology.
  8. Laszlo, H., 2013. Improvement of Batch Distillation Separation of Azeotropic Mixtures, Phd thesis, Budapest University of Technology and Economics.
  9. Luben, W.L., L.A. Wenzel, 1988. Chemical process analysis, Prentice-Hall International Series, New Jersey.
  10. Managobinda, B., 2010. VLE modeling Using Unifac Group Contribution Method and its application in Distillation Column Design and Steady State Simulation, Dissertation for Bachelor thesis, National Institute of Technology, Rourkela.
  11. Mohamad Azamudin, I., 2010. Effects of Temperature On Vapor Liquid Equilibrium Of Mtbe-Methanol Mixtures, Bachelor thesis, University Malaysia Pahang.
  12. Narayanan, K.V., 2004. A Textbook of Chemical Engineering Thermodynamics, Prentice Hall India Learning Private Limited.
  13. Ngema, P. T., 2010. Separation process for high purity ethanol production, Dissertation for the M.S. Degree, Durban University of Technology.
  14. Philip Jackson, L., A. Richard Wilsak, 1995. Thermodynamic consistency tests based on the Gibbs-Duhem equation applied to isothermal, binary vapour-liquid equilibrium data evaluation and model testing, Fluid Phase Equilibria, 103 (2): 155-197.
  15. Rao, Y. V. C., 1997. Chemical Engineering Thermodynamics, Universities Press India Limited, Hyderabad.
  16. Redlich, O., A.T. Kister, 1948. Algebraic Representation of Thermodynamic Properties and the Classification of Solutions, Industrial and Engineering Chemistry, 40 (2): 345-348.
  17. Renon, H., J.M. Prausnitz, 1968. Local Compositions in Thermodynamic Excess Functions for Liquid Mixtures, Journal of American Institute of Chemical Engineers, 14: 135-144.
  18. Sabarathinam, P.L., B. Sivaprakash, 2002. Theoretically consistent modified Local composition and Flory-huggins equations in VLE data prediction, Mtech Thesis, Annamalai University.
  19. Seader, J. D., J. Henley, 2006. Separation process Principles, John Wiley and Sons Publication, New Jersey.
  20. Swietoslawski, W., 1963. Azeotropy and Polyazeotropy, Oxford Pergamon Press, London.
  21. Vivek Julka, Madhura Chiplunkar, L. O. Young, 2009. Selection Entariner for Azeotropic Distillation, Chemical Engineering Progress, 47-53.

Publication Details

Published in : Volume 4 | Issue 1 | January-February 2018
Date of Publication : 2018-02-28
License:  This work is licensed under a Creative Commons Attribution 4.0 International License.
Page(s) : 425-436
Manuscript Number : IJSRSET184174
Publisher : Technoscience Academy

Print ISSN : 2395-1990, Online ISSN : 2394-4099

Cite This Article :

Manojkumar M. S, B. Sivaprakash, " Estimation of Thermodynamic Models for Azeotropic Systems Using Data Assessment and Thermodynamic Consistency Test, International Journal of Scientific Research in Science, Engineering and Technology(IJSRSET), Print ISSN : 2395-1990, Online ISSN : 2394-4099, Volume 4, Issue 1, pp.425-436, January-February-2018.
Journal URL :

Article Preview